JPH0920626A - Cosmetic material composition for hair - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cosmetic material composition for the hair having an excellent solubility to water, hair washing property, hair grooming property and feeling in its use. SOLUTION: This cosmetic material composition for the hair contains 0.1-10wt.% specific amphoteric ionic polymer and 99.9-90wt.% medium for the cosmetic material containing water as a major component. The amphoteric ionic polymer is a copolymer consisting of 45-95wt.% amphoteric structural unit of formula I (R<1> is H or methyl; R<2> , R<5> are each a 1-4C alkylene; R<3> , R<4> are each a 1-4C alkyl; A is O or NH; B is COO, PHO3 or SO3 ) with 55-5wt.% ester structural unit of formula II (R<6> is H or methyl; R<7> is a 1-4C alkyl) and having 10,000-500,000 mean molecular weight. The water content is >=60wt.% in the cosmetic material composition for the hair. It is preferable to prepare a foaming hair conditioner, a pump-type spray containing water, a compressed gas-type hair spray containing water, a setting lotion, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a hair cosmetic composition, more specifically,
The present invention relates to a hair cosmetic composition containing a specific zwitterionic polymer, which has excellent water solubility, and has excellent hair washability, hair styling property, and feeling in use.

[0002]

2. Description of the Related Art Acrylic acid is used as a hairdressing polymer.
Anionic polymer, which is a copolymer containing a neutralized product of vinylcarboxylic acid such as methacrylic acid, crotonic acid, maleic acid, etc. as a hydrophilic component, nonionic polymer which is a copolymer containing vinylpyrrolidone etc. as a hydrophilic component, and carboxy. Zwitterionic polymers, which are copolymers having a betaine moiety as a hydrophilic group, are known. Among them, the zwitterionic polymer is known as a polymer for hair styling which is excellent in terms of affinity with hair and performance such as setting power, and a tertiary amine-containing (meth) acrylic acid ester-based unsaturated monomer (a ) 20-6
0% by weight, (meth) acrylic acid alkyl ester (b) having an alkyl group having 1 to 4 carbon atoms and 12 carbon atoms
Hairdressing comprising a zwitterionic polymer obtained by zwitterionizing a terpolymer with 30 to 70% by weight of a mixture with a (meth) acrylic acid alkyl ester (c) having 18 to 18 alkyl groups with a halogenated acetate. Resin (Japanese Patent Laid-Open No. 51-9
732 and JP-A-55-104209) have been put to practical use. Hereinafter, “(meth) acrylic acid alkyl ester” is a term that collectively refers to acrylic acid alkyl ester and methacrylic acid alkyl ester.

Further, in addition to these excellent performances, combability,
A tertiary amine-containing (meth) acrylic acid ester unsaturated monomer 65 to 90% by weight and a carbon number 12 to which imparts a conditioning effect such as smoothness and has a good usability.
A hair styling resin comprising a zwitterionic polymer obtained by zwitterionizing a copolymer with an alkyl (meth) acrylate having 24 alkyl groups in an amount of 10 to 35% by weight with a halogenated acetate is also known. Sho 61-25880
No. 4).

However, the zwitterionic polymer using a (meth) acrylic acid alkyl ester having an alkyl group having 12 or more carbon atoms as the above-mentioned hydrophobic monomer is diluted with water when preparing a hair cosmetic composition. There is a difficult problem, and it is necessary to take a step of dissolving it in water heated to 50 to 70 ° C. Further, when a hair styling cosmetic composition containing this zwitterionic polymer is applied to hair for use, the dry film obtained has a soft finish, and therefore it is unsatisfactory when a hard feel is desired. Further, in a hair mousse cosmetic which is ejected in the form of foam (mousse), it is desired to improve the washability of the film.

[0005]

DISCLOSURE OF THE INVENTION In order to solve the problems of the conventional zwitterionic polymer of the cosmetic base material for hair, the present invention is to investigate the type and ratio of the comonomer of the zwitterionic polymer. Thus, when preparing a hair cosmetic composition, the problem of being difficult to dilute with water is solved, and when applied as a composition to hair, it has sufficient hair washability, has a hard feel, and has a good feel. It is intended to provide a hair cosmetic composition having a hair styling property.

[0006]

The first aspect of the present invention is to provide (a) 45 to 95% by weight of a zwitterionic structural unit represented by the following formula (I) and (b) an ester represented by the following formula (II). Structural unit 5
A copolymer comprising 5 to 5% by weight, wherein the water-soluble copolymer having a weight average molecular weight of 10,000 to 500,000 is 0.1 to 10% by weight, and water is the main component. The present invention provides a hair cosmetic composition containing 99.9 to 90% by weight of a cosmetic medium (however, 60% by weight or more of water is contained in the hair cosmetic composition).

[0007]

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(In the formula, R ¹ is a hydrogen atom or a methyl group,
R ² and R ⁵ are each an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and A is an —O— or —NH— group. ; B
Represents a —COO group, a —PHO ₃ group, or a —SO ₃ group. )

[0009]

[Chemical 6]

(In the formula, R ⁶ is a hydrogen atom or a methyl group,
R ⁷ represents an alkyl group having 1 to 4 carbon atoms. The second aspect of the present invention is (A) (a) 45 to 95% by weight of the zwitterionic structural unit represented by the following formula (I), and (b) the following formula (II).
A copolymer consisting of 55 to 5% by weight of an ester structural unit represented by the following formula, wherein the weight average molecular weight of the copolymer is 10,
000-500,000 water-soluble copolymer 0.1
10% by weight, (B) nonionic surfactant
0.1-5% by weight (C) Liquefied gas
3-25% by weight (D) Water-soluble solvent mainly composed of water
60% by weight to the balance The present invention provides a hair cosmetic composition which contains the above-mentioned components (A), (B), (C) and (D) and can be ejected in a foamy form.

[0011]

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(Wherein R ¹ represents a hydrogen atom or a methyl group;
R ² and R ⁵ are each an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and A is an —O— or —NH— group. ; B
Represents a —COO group, a —PHO ₃ group, or a —SO ₃ group. )

[0013]

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(In the formula, R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ represents an alkyl group having 1 to 4 carbon atoms. (Summary of the Invention) Zwitterionic Copolymer (A) The water-soluble copolymer (a) comprising the structural unit (I) and the structural unit (II) of the present invention is a zwitterionic compound represented by the formula (III). It is produced by copolymerizing an unsaturated monomer and an alkyl (meth) acrylic acid ester having an alkyl group represented by formula (IV) and having 1 to 4 carbon atoms.

[0015]

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Wherein R ¹ is a hydrogen atom or a methyl group;
² and R ⁵ are each an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ are alkyl groups each having 1 to 4 carbon atoms, A is an —O— or —NH— group; B Is
-COO group, -PHO ₃ group, or an -SO ₃ group. )

[0017]

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Further, if necessary, the polymerizable monomer described below may be used in the range of 20% by weight or less based on the total amount of all monomers.
Further, in place of the zwitterionic unsaturated monomer represented by the formula (III), the precursor thereof is in the form of an amine derivative or an amide derivative of (meth) acrylic acid represented by the following general formula (V). After the copolymerization, a zwitterionized copolymer can be obtained by using an amphoteric agent.

[0019]

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(In the formula, R ^{1 to} R ⁴ and A have the same meanings as in the general formula (III).) Zwitterionic unsaturated monomer: Zwitterionic unsaturation represented by the formula (III) Examples of the monomer include N- (meth) acryloyloxyethyl N, N-dimethylammonium N.
-Methylcarboxylate, N- (meth) acryloylamidopropyl N, N-dimethylammonium N-
Methyl carboxylate, N- (meth) acryloyloxyethyl N, N-diethylammonium N-propane sulfonate, etc. can be mentioned. Further, an amine derivative of (meth) acrylic acid represented by the formula (V),
Alternatively, specific examples of the amide derivative include, for example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth).
There are acrylamide and diethylaminopropyl (meth) acrylamide.

Examples of the amphoteric agent include sodium monobromide acetate, potassium monochloroacetate, lithium monochloropropionate, or monochloroacetic acid and ammonia, 2-amino-2-methyl-1-propanol, triethanolamine or the like. Salts of monohalogenated fatty acids such as hydrates; lactones such as propiolactone; sartones such as propane sultone and butane sultone; and phosphides such as propio phosphide.

The amount of the zwitterionic unsaturated monomer used is 45 to 95% by weight, preferably 50 to 90% by weight, based on the total monomers.
% By weight. When it is less than 45% by weight, the resulting zwitterionic polymer becomes poorly soluble in water, which causes a problem that it is difficult to dilute with water when preparing a hair cosmetic composition, and it becomes difficult to remove it with water during washing. Moreover, the affinity for hair due to the zwitterionic nature of this resin is reduced, resulting in
There are problems such as occurrence of flaking and deterioration of antistatic property. If it exceeds 95% by weight, the resulting amphoteric ionic polymer resin has poor moisture resistance, and the hair setting power under high temperature and high humidity becomes insufficient. There is also a problem that the hardness of the polymer film is lowered.

Having an alkyl group having 1 to 4 carbon atoms (
A) alkyl acrylate: Specific examples of the (meth) acrylate represented by the formula (IV) include methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, There are (meth) acrylic acid alkyl esters having an alkyl group having 1 to 4 carbon atoms such as tertiary butyl (meth) acrylate.

The unsaturated monomer represented by the formula (IV) is used in an amount of 5 to 55% by weight, preferably 10% by weight, based on all monomers.
５０50% by weight. If the amount is less than 5% by weight, the resulting zwitterionic copolymer film has a problem that the hardness is insufficient and the film becomes sticky. When it exceeds 55% by weight, the resulting zwitterionic copolymer becomes poorly soluble in water, which causes a problem of being difficult to dilute with water when preparing a hair cosmetic composition, and also makes it difficult to remove it by washing with water. Become. Further, there is a problem that the resulting zwitterionic copolymer film (film) becomes brittle.

When the number of carbon atoms of the alkyl group of the (meth) acrylic acid alkyl ester exceeds 4, the resulting zwitterionic polymer becomes sparingly soluble in water, and it becomes difficult to wash and remove it when washing hair. Furthermore, since the resulting amphoteric polymer resin film has a problem of becoming soft, (meth) acrylic acid alkyl ester having an alkyl group having 5 or more carbon atoms is not substantially used. Substantially what is meant here is
The ratio of the constitutional units is 3% by weight based on all monomers.
It means the following.

Specific examples of the (meth) acrylic acid alkyl ester having an alkyl group having 5 or more carbon atoms include:
For example, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, oleyl (meth).
There are acrylate, cyclohexyl (meth) acrylate and the like.

Other unsaturated monomers: In addition to the above-mentioned unsaturated monomers, a range which does not lower the water solubility of the zwitterionic copolymer obtained as necessary, for example, 20% by weight based on the total monomers. Other unsaturated monomers can be used in the range of less than or equal to%. By appropriately selecting this unsaturated monomer to be used, it is possible to impart appropriate flexibility and hardness to the zwitterionic copolymer finally obtained to control the feel and the like.

Specific examples of the unsaturated monomer include, for example, acrylonitrile, hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, tetrahydrofuran. Furyl (meth) acrylate, ethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, 1,3-
(Meth) acrylic derivatives such as butylene glycol di (meth) acrylate and diacetone acrylamide; aromatic unsaturated monomers such as styrene, chlorostyrene, vinyltoluene; N-vinylpyrrolidone, N-vinylcaprolactam, vinyl acetate, etc. Vinyl unsaturated monomers and the like.

The above-mentioned copolymerization of unsaturated monomers can be carried out by a known radical polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method, but a preferable polymerization method is a solution polymerization method. That is, a predetermined amount of each polymerizable unsaturated monomer is dissolved in a solvent, a polymerization initiator is added, and the mixture is heated and stirred under a nitrogen stream. Examples of the polymerization initiator include peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile (abbreviated as AIBN) and azobisdimethylvaleronitrile (abbreviated as ADVN).

The solvent is preferably water; alcohols such as methanol, ethanol, isopropanol, ethylene glycol and butyl cellosolve; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; acetic acid esters such as methyl acetate and ethyl acetate. Two or more kinds of these solvents may be appropriately mixed and used. The amount of solvent used is such that the resin concentration in the produced copolymer solution is 10 to 65.
%.

In the polymerization, the monomer and the polymerization initiator are
It is usual that all kinds and all amounts thereof are present from the beginning of the polymerization, but a divided addition method can be used for those kinds and / or amounts. The weight average molecular weight of the obtained copolymer is 10,000 to 500,000.
The range is 0, preferably 30,000 to 300,000. The molecular weight can be controlled by appropriately selecting the polymerization conditions such as the polymerization temperature, the type and amount of the polymerization initiator, the amount of the chain transfer solvent such as ethanol and isopropanol, the amount of the chain transfer agent such as butyl mercaptan and lauryl mercaptan. This can be done by

As described above, after the copolymerization is carried out in the form of an amine derivative or an amide derivative of (meth) acrylic acid which is a precursor thereof, instead of the zwitterionic unsaturated monomer,
When the amphoteric agent is used to obtain a zwitterionic copolymer, the amount of the amphoteric agent used is 70 to 1 in equimolar stoichiometry.
30% is preferred. In this amphoteric reaction, when an amphoteric agent that produces a by-product salt such as sodium monobromide acetate or potassium monochloroacetate is used as the amphoteric agent, the by-product salt is filtered and centrifuged as necessary. It is also possible to separate and remove it with an ion exchange treatment, and further to remove the dissolved salt by ion exchange treatment (JP-A-55-104209 and JP-A-61).
-258804 publication). The obtained zwitterionic copolymer may be used as it is as a solution of the produced copolymer, or may be obtained by removing the solvent of the produced copolymer solution by evaporation or by precipitating the copolymer by using a poor solvent. The solid form may be used as it is.

The odor of the zwitterionic copolymer obtained, if necessary, can be improved by azeotropically distilling the odorous component with a solvent in a solution state or by adsorbing and removing it with an adsorbent such as activated carbon, activated clay or zeolite. Etc. In the solid state, it can be carried out by heating under reduced pressure and extraction with a solvent such as ethers. The zwitterionic copolymer has excellent water solubility, and is 40% by weight of the zwitterionic copolymer at 5 ° C.
The solubility of the alcohol solution in 1 liter of water at 5 ° C. (hereinafter referred to as “cold water solubility”) is 30 g / l or more,
It is preferably 50 g / l or more.

(Hair cosmetic composition) In the hair cosmetic composition of the present invention, the zwitterionic copolymer obtained as described above is mixed in a cosmetic medium, and 0.1% of the composition is used. ~ 1
A hair cosmetic composition containing 0% by weight, which is excellent in hair washability, hair styling property, and feeling in use. Furthermore, when preparing a hair cosmetic composition, a water-containing cosmetic composition in which the cosmetic medium is composed of at least 60% by weight of water is preferable because it is excellent in dilutability with water.

When the content is less than 0.1% by weight, it is insufficient to exert the effect of the polymer of the present invention when used as a hair cosmetic, and when it exceeds 10% by weight, amphoteric ions for hair. The amount of the adhered copolymer increases, conversely impairing the hair washability and increasing flaking. The medium for cosmetics means a solvent which is a known medium constituting various forms of hair cosmetics, liquefied gas and compressed gas used as a propellant, and known additives.
Specific examples of the solvent include water, hydrophilic solvents such as ethyl alcohol, isopropyl alcohol, and ethylene glycol such as dihydric alcohols, and hydrophobic solvents such as isoparaffin and cyclic silicone.

The liquefied gas and the compressed gas include liquefied petroleum gas, liquefied gas such as dimethyl ether and halogenated hydrocarbon, and compressed gas such as air, carbon dioxide gas and nitrogen gas. Addition of known additives means, for example, anionic activator, cationic activator, nonionic activator, surfactant such as zwitterionic activator, and foaming agent,
There are thickeners, hadrotropes, emulsions, conditioning agents including silicone polymers and their chemically modified substances, oils and fats, moisturizers, plasticizers, coloring agents such as dyes and pigments, bactericides, and fragrances.

In the hair cosmetic composition of the present invention, a known cationic, anionic or nonionic natural polymer, a natural modified polymer or a synthetic polymer which has been conventionally used is used in combination. Good. The hair cosmetics of the present invention include mascaras, aerosol-type hair sprays, pump-type hair sprays, foam-like hair styling agents, set lotions, hair liquids, hair gels, hair creams, hair oils, etc. Means hair cosmetics. A preferred application is a water-containing system in which the cosmetic medium is composed of at least 60% by weight of water because the zwitterionic copolymer is excellent in dilutability with water when preparing a hair cosmetic composition. Examples include cosmetics such as foam hair styling products, pump-type water-containing hair sprays, compressed gas-type water-containing hair sprays, and set lotions.

The composition of a particularly preferred hair styling product will be disclosed below. (A) Water-soluble zwitterionic copolymer 0.1 to 10% by weight (B) Nonionic surfactant 0.1 to 5% by weight (C) Liquefied gas 3 to 25% by weight (D) Mainly water Water-soluble solvent 60% by weight to the balance Hair cosmetics containing the above components (A), (B), (C) and (D) (however, water accounts for 60% by weight or more in the cosmetics). ). Examples of the nonionic surfactant as the component (B) include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene alkylphenyl ether. Examples thereof include oxyethylene castor oil, polyoxyethylene hydrogenated castor oil, and fatty acid alkanolamide. Above (A),
In addition to the components (B), (C) and (D), the above-mentioned oils and fats, fragrances, colorants, bactericides, humectants and the like may be blended depending on the purpose.

The hair cosmetic composition of the present invention is excellent in hair washability, hair styling property, and feeling in use. Here, the hair styling property means that the hair styled (set) by the hair cosmetic is
It is the property that the hair styling is maintained even in a hot and humid atmosphere. In addition, "excellent in use feeling" means that the hair conditioned by the hair cosmetic composition has a hard feel, and also has good combability and smooth feel.

[0040]

EXAMPLES The present invention will be described in more detail with reference to experimental examples. Parts and% in the production examples are based on the weight, and parts and% in the examples are based on the weight of the active ingredient.

<Production Example 1> In a five-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, a glass tube for nitrogen substitution, and a stirrer, dimethylaminoethyl methacrylate: 45 parts, methyl methacrylate: 30 parts , Isobutyl methacrylate: 25 parts, absolute ethanol: 82 parts, ADVN: 0.2 part were added, and the temperature was 60 ° C. under a nitrogen stream.
And after 4 hours, add AIBN: 0.6 part,
The temperature was raised to 0 ° C., and the temperature was kept at the same temperature for 4 hours under nitrogen stream to carry out a copolymerization reaction.

Next, a 40% anhydrous ethanol suspension of a potassium hydroxide neutralized product of monochloroacetic acid in an equimolar amount to dimethylaminoethyl methacrylate was added dropwise to the five-necked flask with a dropping funnel, and further under a nitrogen stream. The mixture was heated at reflux at 0 ° C. for 12 hours for amphoteric reaction. The obtained viscous suspension was filtered with a filter, and the filtrate was regenerated. A cation exchange resin from Mitsubishi Chemical Co., Ltd. ("DIAION PK-220" was regenerated and the system was replaced with absolute ethanol). Was passed through the column filled with the anion-exchange resin, and then the column was filled with a regenerated anion exchange resin ("DIAION PA-416" after regeneration, and the system was replaced with absolute ethanol).

Next, the solvent was removed under reduced pressure at 70 ° C. to obtain a solid. The solid was crushed, washed well with diethyl ether, and dried well at 70 ° C. under reduced pressure to obtain a solid. To 40 parts of the obtained solid matter, 60 parts of ethanol was added and dissolved to obtain a solution having a polymer concentration of 40%. The obtained polymer (cold water solubility 125 g / l) is designated as "P-1".
The composition ratio of the obtained polymer is (I) a zwitterionic unsaturated monomer unit / (II) a (meth) acrylic acid alkyl ester unit having an alkyl group having 1 to 4 carbon atoms / (III) arbitrary polymerization When expressed as a ratio of a polyunsaturated monomer (hereinafter (I) / (I
I) / (III)) and 53/47/0. The weight average molecular weight of the polymer was 140,000 when measured by gel permeation chromatography (hereinafter abbreviated as GPC) using polystyrene as a standard substance.

Production Example 2 The same operation as in Production Example 1 was repeated except that the unsaturated monomers were diethylaminoethyl methacrylate: 70 parts, methyl acrylate: 20 parts, and butyl methacrylate: 10 parts, and the polymer concentration was 40%. A solution of The polymer thus obtained (cold water solubility
125 g / l or more) is designated as "P-2". The composition ratio of the obtained polymer is (I) / (II) / (III) = 76/24/0.
It is. The weight average molecular weight of the polymer is 150,0.
It was 00.

<Production Example 3> N-methacryloyloxyethyl N, N- was placed in the five-necked flask used in Production Example 1.
Dimethyl ammonium N-methyl carboxylate:
65 parts, ethyl methacrylate: 20 parts, isopropyl methacrylate: 15 parts, and absolute ethanol: 100
Parts, ADVN: 0.8 parts, and under nitrogen stream 8
The mixture was heated under reflux at 0 ° C., and after 2 hours, AIBN (0.4 parts) and absolute ethanol (50 parts) were added, and the mixture was further added under a nitrogen stream 6
Copolymerize for an hour, add about 10 parts of absolute ethanol,
250 parts of an ethanol solution having a polymer concentration of 40% was obtained.
The obtained polymer (cold water solubility 125 g / l or more) was treated with "P
-3 ". The composition ratio of the obtained polymer was (I) / (I
I) / (III) = 65/35/0. The weight average molecular weight of the polymer was 40,000.

<Production Example 4> In the five-necked flask used in Production Example 1, dimethylaminoethyl methacrylate: 50 was added.
Parts, methyl methacrylate: 25 parts, tertiary butyl acrylate: 25 parts, and isopropanol: 82
Parts, add AIBN: 0.2 parts, and under a nitrogen stream 6
Heat at 0 ° C for 10 hours, then add AIBN (0.2 parts) and further heat at 60 ° C for 5 hours under a nitrogen stream, then at 80 ° C.
The mixture was heated to reflux for 6 hours.

Next, a 40% isopropanol solution of propanesartone in an equimolar amount to dimethylaminoethyl methacrylate was dropped into the five-necked flask with a dropping funnel, and the mixture was heated under reflux at 80 ° C. under a nitrogen stream for 4 hours for amphoteric sex. After the oxidization reaction, isopropanol was added to give a polymer concentration of 4
340 parts of a 0% isopropanol solution were obtained. The obtained polymer (cold water solubility 125 g / l or more) is designated as "P-4". The composition ratio of the obtained polymer was (I) / (II) / (II
I) = 64/36/0. The weight average molecular weight of the polymer is 25 when measured by GPC as in Production Example 1.
It was 0000.

<Production Example 5> N-methacryloyloxyethyl N, N-diethylammonium N-methylcarboxylate in the five-necked flask used in Production Example 1 was 5:
5 parts, butyl methacrylate: 30 parts, N-vinylpyrrolidone: 15 parts, and absolute ethanol: 100 parts were added, AIBN: 0.6 part was added, and the mixture was heated under reflux at 80 ° C. under a nitrogen stream and after 2 hours AIBN. : 0.6 part, and anhydrous ethanol: 50 parts were added, and copolymerization was further performed for 6 hours in a nitrogen stream. About 10 parts of anhydrous ethanol was added to obtain 250 parts of an ethanol solution having a polymer concentration of 40%. The obtained polymer (cold water solubility 125 g / l or more) was designated as "P-5".
And The composition ratio of the obtained polymer is (I) / (II) /
(III) = 55/30/15. The weight average molecular weight of the polymer was 70,000.

<Production Example 6> The procedure of Production Example 1 was repeated except that the unsaturated monomer was dimethylaminoethyl methacrylate: 45 parts, isobutyl methacrylate: 25 parts, and stearyl methacrylate: 30 parts, and the polymer concentration was 4 parts.
A 0% solution was obtained. Polymer obtained (cold water solubility 20 g
/ L) is defined as "P-6". The composition ratio of the obtained polymer is (I) / (II) / stearyl methacrylate unit =
It is 53/21/26. The weight average molecular weight of the polymer was 140,000.

<Production Example 7> The procedure of Production Example 1 was repeated except that the unsaturated monomers were dimethylaminoethyl methacrylate: 30 parts, methyl methacrylate: 35 parts and butyl methacrylate: 35 parts, and the polymer concentration was 40. % Solution was obtained. The obtained polymer (cold water solubility: less than 20 g / l) is designated as "P-7". The composition ratio of the obtained polymer is
(I) / (II) / (III) = 37/63/0. still,
The weight average molecular weight of the polymer was 140,000.

<Production Example 8> N-methacryloyloxyethyl N, N- was placed in the five-necked flask used in Production Example 1.
Dimethyl ammonium N-methyl carboxylate:
100 parts and absolute ethanol: 100 parts are added, AI
BN: 0.6 parts was added, and the mixture was refluxed and heated at 80 ° C. under a nitrogen stream, and 2 hours later, AIBN: 0.6 part and anhydrous ethanol: 50 parts were added, and polymerization was further performed under a nitrogen stream for 6 hours. Add about 10 parts of ethanol to give a polymer concentration of 40
% Of ethanol solution was obtained. The obtained polymer (cold water solubility: 125 g / l or more) is designated as "P-8". The composition ratio of the obtained polymer was (I) / (II) / (III) = 10.
It is 0/0/0. The weight average molecular weight of the polymer is
It was 70,000.

<Example 1> When "P-1" obtained in Production Example 1 was diluted with water at 20 ° C, it could be easily diluted.
In addition, when the following formula was used to prepare a hump-type water-containing hair spray and a foamy hair styling cosmetic composition, and when applied to hair, good setting power was exhibited even under high temperature and high humidity. The applied hair had a good hard feel and had good washability. The results are shown in Table 1.

(1) Pump type water-containing hair spray (parts by weight) Copolymer solution 20 (however, zwitterionic copolymer concentration is 5) Water 65 Ethanol Residue (15) ──────────── ─────────────────────── (total) 100

(2) Pump-type water-containing hair spray (parts by weight) Copolymer solution 7.5 (however, zwitterionic copolymer concentration is 3) Water 65 Ethanol Residual (27.5) ─────── ─────────────────────────── (total) 100

(3) Foamed hair styling cosmetic (parts by weight) Copolymer solution 12.5 (however, zwitterionic copolymer concentration is 5) Nikkor HCO-50 (* 1) 0.8 Nikkor BL-9EX ( * 2) 0.2 Amizole CDE (* 3) 0.3 Polymer JR-400 (* 4) 0.2 Silicone SH3749 (* 5) 0.5 Ethanol (in copolymer solution) 7.5 Liquefied petroleum gas (LPG) 8 Water residue (70) ────────────────────────────────── (total) 100 (* 1 ) Ethylene oxide adduct of hydrogenated castor oil; Nikko Chemical Co., Ltd. (* 2) Ethylene oxide adduct of lauryl alcohol; Kawaken Fine Chemical Co., Ltd. (* 3) Palm oil fatty acid diethanolamide; Kawaken Fine Chemical Co., Ltd. (* 4) Cation Ether cellulose; manufactured by Union Carbide Corporation (* 5) silicone polyethers; manufactured by Dow Corning Toray Co., Ltd.

<Examples 2 to 5> Copolymer solution "P-1"
A cosmetic was prepared and evaluated in the same manner as in Example 1 except that "P-2", "P-3", "P-4" or "P-5" was used instead of. As shown in Table 1, the cosmetic was excellent in water dilutability and showed good performance as a hair cosmetic.

<Comparative Examples 1 to 3> Example 1 except that "P-6", "P-7" or "P-8" was used in place of the zwitterionic copolymer solution "P-1". In the same manner, cosmetics were prepared and evaluated. As shown in Table 1, there were insufficient performances or problems in any of the evaluation items of water dilutability, setting power under high temperature and high humidity, feel of coated hair, or hair washability.

<Evaluation Method> 1) Water Dilutability To 1 liter of pure water controlled at 5 ° C., 25 parts of each of the polymer solutions “P-1” to “P-8” at 5 ° C. were added and 3
Stir at 00 rpm for 5 minutes, and observe the solution state 15 minutes after the stirring is stopped. ○: A homogeneous solution is obtained. Δ: Some insoluble polymer remains. ×: Polymer deposits.

2) Setting power 23 cm, 2 g of straight hair is applied in a fixed amount on the hair in the form of a pump-type water-containing hair spray and a foamy hair styling agent,
Immediately roll it in a curler with a diameter of 2 cm to dry it. Next, the hair removed from the curler is hung in a constant temperature and humidity room at a temperature of 30 ° C. and a relative humidity of 95%, the elongation of the hair after 3 hours is measured, and the curl retention force (%) is assigned to the curl retention formula. Ask.

3) Feeling Using a pump type water-containing hair spray (resin concentration: 5%), the curled hair obtained was operated in the same manner as the setting force, and the resulting curled hair was kept at a temperature of 23 ° C. and a relative humidity of 60%. Evaluate the feeling when touched with a finger after leaving it under the conditions of. ○ ……… Has smooth slipperiness. △ ……… Slightly caught. ×: There is a feeling of sticking or stickiness.

4) Hardness The curled hair obtained by operating in the same manner as the setting force using a pump-type hydrous hair spray (polymer concentration: 3%) was used, and the temperature was 23 ° C. and the relative humidity was 60%. The curability (elasticity) when the curl is crushed with a finger is evaluated under the condition of. ○ ……… Good elasticity. ×: No elasticity.

5) Hair Washability A curled hair obtained by operating in the same manner as the setting force using a hydrous hair spray of a pump system (polymer concentration: 5%) was used, and 3 mol of ethylene oxide of dodecyl alcohol kept at 40 ° C. Wash with a 10% by weight aqueous solution of the adduct sulfate and rinse well with warm water at 40 ° C. Air-dry, visually evaluate the polymer remaining on the hair and visually. ○ ……… The polymer has been removed. △ ……… Some polymer remained. ×: Polymer remains.

[0063]

[Table 1]

[0064]

EFFECTS OF THE INVENTION Hair cosmetics can be easily prepared, and the setting power,
Gives a hair cosmetic having excellent hair washability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kayo Ito, Tokamachi, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. Yokkaichi Research Institute

Claims (2)

[Claims] 1. A copolymer comprising (a) 45 to 95% by weight of a zwitterionic structural unit represented by the following formula (I) and (b) 55 to 5% by weight of an ester structural unit represented by the following formula (II). A polymer having a weight average molecular weight of 10,000
A hair cosmetic composition containing 0.1 to 10% by weight of a water-soluble zwitterionic copolymer of about 500,000 and 99.9 to 90% by weight of a water-based cosmetic medium (however, Water accounts for 60% by weight or more in the hair cosmetic composition). Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ⁵
Each represents an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ each represent an alkyl group having 1 to 4 carbon atoms, A represents a —O— or —NH— group; COO
Group shown, -PHO ₃ group, or a -SO ₃ group. ) (In the formula, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 4 carbon atoms.) 2. (A) (a) 45 to 95% by weight of the zwitterionic structural unit represented by the following formula (I), and (b) the following formula (II):
A copolymer consisting of 55 to 5% by weight of an ester structural unit represented by the following formula, wherein the weight average molecular weight of the copolymer is 10,
Water-soluble zwitterionic copolymer of 000 to 500,000 0.1 to 10% by weight, (B) nonionic surfactant
0.1-5% by weight (C) Liquefied gas
3-25% by weight (D) Water-soluble solvent mainly composed of water
60% by weight to the balance 60% by weight to the balance A hair cosmetic composition that can be jetted in the form of a foam containing the above-mentioned components (A), (B), (C), and (D) (however, water is 60 in the hair cosmetic composition; Contains more than wt%). Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ⁵
Each represents an alkylene group having 1 to 4 carbon atoms, R ³ and R ⁴ each represent an alkyl group having 1 to 4 carbon atoms, A represents a —O— or —NH— group; COO
Group shown, -PHO ₃ group, or a -SO ₃ group. ) [Chemical 4] (In the formula, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 4 carbon atoms.)